Super-macroporous polymeric microspheres and preparation method thereof

Abstract

The invention provides a preparation method of super-macroporous polymeric microspheres and a product thereof. The method is characterized in that adding high content of surfactant into an oil phase containing a monomer and dispersing the oil phase containing the monomer and the surfactant into an aqueous phase. Super-macroporous microspheres are obtained by means of suspension polymerization. In the interior of the microspheres, 10-60% of the pores are distributed in a range of 500-900 nm. The microspheres have a particle diameter of 1-200 μm and a porosity of 30%-90%. The product is suitable for being used as a stationary phase matrix in liquid chromatography, a carrier for high performance catalysts and a high performance adsorbent, and especially, being used as a separation medium for separating biomacromolecules.

The invention claimed is: 
     
       1. A method for preparing super-macroporous polymeric microspheres, which in the interior thereof comprising micropores with a pore diameter of 10-200 nm and super macropores with a pore diameter of 500-900 nm, wherein the super macropores comprise 10-60% of the inner pore volume of the microsphere, said method comprising:
 into a mixture of a monomer and a cross-linking agent, adding an initiator, a diluent and an oil-soluble surfactant to formulate an oil phase, wherein the surfactant forms a large amount of reverse micelles in the oil phase; 
 mixing the oil phase and an aqueous phase to polymerize the monomer, wherein the reverse micelles of the surfactant in the liquid droplets of the oil phase absorb water spontaneously and swell into continuous channels; and 
 performing separation and drying to prepare the super-macroporous polymeric microspheres. 
 
     
     
       2. The method according to  claim 1 , wherein the surfactant is selected from the group consisting of sorbitan fatty acid ester, polyglycerol fatty acid ester, polyoxyethylene fatty acid ester, alkyl phenol polyoxyethylene ethers, and mixtures thereof. 
     
     
       3. The method according to  claim 1 , wherein the surfactant is sorbitan monooleate. 
     
     
       4. The method according to  claim 1 , wherein the surfactant is para-octyl phenol polyoxyethylene ether. 
     
     
       5. The method according to  claim 1 , wherein the mass content of the surfactant in the oil phase is 5%-80%. 
     
     
       6. The method according to  claim 1 , wherein the mass content of the surfactant in the oil phase is 25%-60%. 
     
     
       7. The method according to  claim 1 , wherein the monomer is anyone selected from the group consisting of oil-soluble vinyl monomers and any mixtures thereof. 
     
     
       8. The method according to  claim 1 , wherein the mass content of the monomer in the oil phase is 1%-90%. 
     
     
       9. The method according to  claim 1 , wherein the monomer is at least one selected from the group consisting of ethylene type, styrene type, (meth)acrylic acid type, (meth)acrylate type, (meth)acrylamide type, epoxy type and vinyl acetate type monomers. 
     
     
       10. The method according to  claim 1 , wherein the mass content of the monomer in the oil phase is 25%-45%, the mass content of the cross-linking agent in the oil phase is 10%-45%, the mass content of the diluent in the oil phase is 0%-50%, and the mass content of the initiator in the oil phase is 0.01-10%. 
     
     
       11. The method according to  claim 9 , wherein the cross-linking agent is selected from the group consisting of divinylbenzene (DVB), ethylene dimethacrylate (EGDMA), trimethylolpropane trimethyl acrylate (TRIM) and any mixtures thereof. 
     
     
       12. The method according to  claim 1 , wherein the aqueous phase comprises a water-soluble stabilizer. 
     
     
       13. The method according to  claim 1 , wherein the cross-linking agent is at least one selected from the group consisting of oil-soluble divinyl bearing compounds, trivinyl bearing compounds and any mixture thereof. 
     
     
       14. The method according to  claim 1 , wherein the diluent is at least one selected from the group consisting of paraffins, alcohols, ethers, benzenes, polymers which are soluble in the monomer, and any mixtures thereof. 
     
     
       15. The method according to  claim 1 , the initiator is at least one selected from the group consisting of azo type initiators, peroxide initiators and any mixtures thereof. 
     
     
       16. The method according to  claim 1 , wherein the mass content of the cross-linking agent in the oil phase is 1%-90%. 
     
     
       17. The method according to  claim 1 , wherein the mass content of the diluent in the oil phase is 0%-80%. 
     
     
       18. The method according to  claim 1 , wherein the mass content of the initiator in the oil phase is 0.01%-10%. 
     
     
       19. The method according to  claim 1 , wherein the cross-linking agent is selected from the group consisting of divinyl aromatic compounds, acrylate type compounds and any mixtures thereof. 
     
     
       20. The method according to  claim 1 , wherein the diluent is at least one selected from the group consisting of heptane, dodecane, cetane, iso-octane, dodecyl alcohol, cyclohexanol, n-butanol, petroleum ether, toluene, polystyrene, poly(meth)acrylate, and any mixtures thereof. 
     
     
       21. The method according to  claim 1 , wherein the initiator is at least one selected from the group consisting of benzoyl peroxide, azobisisobutyronitrile, and any mixtures thereof.